Process and material for producing photographic multi-color images



PROCESS AND MATERIAL FOR PRODUCING PHOTOGRAPHIC MULTI-COLOR IMAGES Jacob Joseph .lennen, Antwerp, Belgium, assignor to Gevaert Photo-Producten N. V., Mortsel, Belgium, a company of Belgium- No Drawing. Application December 12, 1950 Serial No. 200,491

Qllaims priority, application Great Britain December 13, 1949 6 Claims. (Cl. 96-5 This invention relates to the manufacture of photographic multi-color images permitting improved color reproduction.

A subtractive multi-color image is. composed of at least two dyestur't images. In the subtractive three-color photography, the dyestuffs should in theory completely absorb the visible light rays in one third of the spectrum and transmit them in the remaining two thirds. The dyestuffs commercially available do not fulfil these spectral requirements. For instance, the blue-green dyestuffs do not sufliciently absorb all red rays as desired, and moreover they show an undesirable absorption of the green and especially blue rays. show an insufficient absorption an undesirable blue-absorption.

In order to compensate the undesirable absorption of a part image, it has been proposed to correct this part image by a complementary image, in the nature of a reversed image, sorption of which both in of green and moreover quality and quantity corresponds as much as possible to the undesirable absorption. This causes an even color deviation all over the image area. in a simple manner, for instance, by-the use of an. adequate color filter while copying or projecting.

Said complementary image may consistof acolored color coupler which remains after color development, or of a dyestuif which, after treatment by the silver dyestuff bleach process, is left in the photographic. material at all points where no silver is or of a dyestuftproduced by azo-coupling or other coupling reaction with the residual color coupler. Since undesirable absorption occurs chiefly in the blue, the complementary image, in most cases, must be yellow. Schinzel, U. S. Patent 2,306,410, describes the formation of blue lignone dyes by oxidation of arylmethyl-pyrazolone, but it is added in this prior patent that the formation of the upper yellow part image in this manner presents diificulties.

An object of my invention is a newprocess for the production of photographic multi-colored images.

A further object is anew process for the production of photographic multi-colored images with improved color rendering.

. Another object is a new process for the production of photographic multi-colored images comprising one or more color-correction images.

Further objects will appear from the following description. I

I. have found that suchcomplementary image may be obtained by the use of a color coupler the residue of which after color development is oxidized to a colored substance.

According to the present invention, a photographic multi-colored image with improved color reproduction properties is obtained as follows:

A photographic material which contains at least two silver halide emulsion layers sensitive to ditfe'rent re- The magenta dyestuffs consisting of a colored substance, the ab- This deviation, however, can be neutralized formed on development,

to States Patent contain another active group,

2,823,993 Patented Feb. 18, 1958 gions of the visible spectrum is exposed to light. At least one of these layers contains a color coupler which is able to form, by reacting with the oxidation product of a. primary aromatic amino developng agent, a dyestuif image strongly absorbing in a part of the spectrum and undesirably less strongly in at least one other part of the spectrum and which by oxidation is converted into a colored substance practically not. absorbing in the first mentioned part of the spectrum but absorbing at least in theother mentioned partof the spectrum. That layer at least, which contains said color coupler, is developed with a primary aromatic amino developing agent and at least the remaining color coupler of this layer is treated in an oxidizing bat In a preferred form of the present invention, the photographic material contains three silver halide emulsion layers sensitive to different regions of the visible spectrum. One of these. layers is sensitive to blue light only and contains a yellow color coupler. Another of these layers is sensitive to green light and contains a magenta color couple'rwhich by oxidation is converted into a yellow' product.- The third layer is sensitive to red light and contains a cyan color coupler which by oxidation is converted intoa yellow, orange or red substance; If one of the red and green sensitive layers is also sensitive to blue light, it is separated from the first mentioned layer by a yellow filter layer.

Color couplers which by oxidation are converted into a colored substance are for. instance the color couplers according to Formula I or a tautomeric form thereof wherein A is O and Z is the atoms necessary to complete an isoor heterocyclic ring or a ring system. Such color couplers are described in my co-pending application Serial No. 128,913, filed November 22, 1949, now Patent No. 2,673,801.

In these color couplers the active group for the color development is believed to be the -CONHNH group. This group is converted in the oxidizing bath into an azo-chromophor. These color couplers may also namely, an ethenol, i. e.

NE NH group or its tautorneric form CH ,-CO-, such as,.for instance, 4- or 7-hydroxy-indazolone. In this case, A may represent NR, R being H, a hydrocarbon radical or' an acylgroup;

Further color couplers which by oxidation. are converted into a colored substance are the compounds according to Formula II amido-pyrazolone.

Further oxidizabl'ecolor couplers which may be used in the performance of thisinvention are the color conplers which contain an urazol or guanazol" group, obtained, for instance, by causing a hydrazo-dicarbonamide to react with a color coupler containing, an amino group,

it or by condensing a guanazofwith a color coupler bearing an aldehyde or an acidic group. correspond to Formula III (III) HIiT-NH A (BA or a tautomeric form thereof wherein A has the same significance as above, R is as R, and R or R is a radical containing a group which is active in color development.

Still further oxidizable color couplers are the acylor cyan acetyl hydrazones of isatine or polyisatine or of other ketones or of aldehydes etc., such as described in Patents 2,375,344 and 2,527,476 and in the co-pending application Serial No. 734,852 of Philibert L. Merckx, now Patent No. 2,540,401 as well as the beta-aryl-hydrazino-beta-imino propionic acid esters wherein the aryl group may also be a heterocyclic group (I1. Am. Chem. Soc. 66 (1944), 1853).

These couplers may be represented by the formula wherein X is CN, acyl, carbalkoxy, or another electronegative group; A is O or NR, R being H, a hydrocarbon radical, or an acyl group; R is H, a hydrocarbon, or a heterocyclic group; R is a heterocyclic group; or R and R together complete an isoor a heterocyclic ring.

Certain compounds according to the Formula IV may also be represented by their tautomeric formula:

XCHzCA-NH-N=C RQH (IVE) wherein X, A, R and R have the same significance as above.

For instance, cyano-acetylhydrazone of mono-bromoisatin (U. S. Patent 2,527,476) may be written according to Formula IV:

CN-CH -C O-NH-NH-C Br or according to Formula IVa:

CN-OHz-C 0NH-N=0 Br It is necessary that groups giving fastness to dilfusion be present in the color couplers.

These color couplers yield after color development red to blue dyestuffs while their oxidation products are yellow to red.

In case the color coupler to be used yields a too strongly absorbing oxidation product, it may be mixed with a color coupler which forms no colored oxidation product.

The oxidizing bath may be a special one, containing, for instance, potassium ferricyanide, potassium bichromate or potassium periodide, or it may be the usual bleach bath for removing the silver.

These oxidizable color couplers may be used in the reversal process as well as in the negative-positive process.

The following examples are given to illustrate my invention, without limiting, however, its scope.

Example 1 13 g. amino-indazolone-hydrochloride, 18 g. octadecenyl succinic acid anhydride and com. pyridine are thoroughly mixed and heated for 30 minutes at a temperature between 170 and 190 C. The product of this reaction is treated thrice with /2 litre of boiling water and each time the water is decanted. Next, l Product Such color couplers is recollected by filtration with suction and recrystallised from methanol. A product corresponding to the FormulaV G. NzN-diethyl-p-phenylene diamine hydrochloride--- 6 Water to 500 com.

G. Potassium carbonate Potassium bromide 2.5

Water to 500 ccm.

After washing for 30 minutes, the silver is removed in the following bath:

Potassium ferricyanide 50 Potassium bromide 3 Water to 1000 ccm.

G. Potassium bichromate 25 Sodium carb n 5 Potassium bromide 5 Water to 1000 ccm.

Example 2 5 g. 3-amino-5-pyrazolone (prepared as described in 11. Am. Chem. Soc. 71 (1949), 987), 19.5 g. octadecenyl succinic acid anhydride and 4 ccm. pyridine are heated for 30 minutes at a temperature between and C. The reaction mixture is poured into warm water. The product precipitated is filtered with suction and recrystallised from a mixture of ethanol and water in a proportion of 3/1. The product obtained corresponds to Formula VI I NH Melting point 145-147" c.

Analysis-N calculated 9.35%, found 9.38% and 1.7 g. of the product is dissolved in 6.8 ccm. of an aqueous solution of potassium hydroxide N, 6.8 ccm. methanol and 34 ccm. water and is added to 100 ccm. of a positive cin emulsion. This emulsion is coated onto a support, exposed and developed for 6 minutes with a solution obtaind by mixing equal parts of the following solutions;

Water to 500 ccm.

After washing for 30 minutes, the silver is removed in the following bath:

G. Potassium ferricyanide 50 Potassium bromide 3 Water to 1000 ccm.

After the removal of the silver, which also oxidizes the coupler residue, the material is again washed for minutes and next fixed for minutes in a bath com-- posed of 250 g. sodium thiosulphate in 1000 ccm. water and finally washed for minutes. A magenta developed image and a yellow complementary'image were obtained;

Example 3 7.4 g. l-hydroxy-Z-naphthoic acid, 2 g. guanazol and 20 ccm. chlorobenzene are heated at 75 C. 1.4 g. phosphorus trichloride are slowly added. The mixture is treated for 30 minutes on the water bath and then on the flame until all hydrochloric acid vapors are eliminated. The mixture is then cooled and filtered with suction. The precipitate is recrystallized in aqueous ethanol (1/1). A product represented by the Formula VII (VII) OH OH I HN--I|\IH CO-NH- o==N-co G. NzN-diethyl-p-phenylene diamine hydrochloride 6 Water to 500. ccm.

G. Potassium carbonate 75 Potassium bromide 2.5

Water to 500 ccm.

After washing for 30 minutes, the silver is removed in the following bath:

G. Potassium ferricyanide Potassium bromide 3 Water to 1000 ccmi After this removal of the silver, which also oxidizes the coupler residue, the material is washed again for 10 minutes and next fixed for 20 minutes in a bath composed of 250 g. sodium thiosulphate in 1000 ccm. water and finally washed for 30 minutes. A blue-green developed image and an orange-red complementary image were obtained.

Example 4 5.3 g. l-hydroxy-Z-naphthoic acid phenyl ester and 4 g,,guanazol are heated for 30 minutes at 180-190 C. After cooling, the mixtureis boiledwith ethanol. Next,

the'residue is filtered with suction and recrystallized: f om pyridine. A product having. the Formula. V111.

(VIII) OH is obtained. Melting point: 295 C., afterwashing with ethanol.

Analysis.N calculated 26.02%, found 26.11%.

5 g. of this product are dissolved in 4 ccm. methanol, 6 ccm. water and 15 ccm. of an aqueous solution of potassium hydroxide N and added to ccm. of a positive cin emulsion. This emulsion is coated onto a support, exposed and developed for 6 minutes with a. solution obtained by mixing equal parts of the following solutions:

G. NzN-diethyl-p-phenylene diamine hydrochloride 6 Water to 500 ccm.

Potassium carbonate Potassium bromide Water to 500 ccm.

After washing for 30 minutes, the. silver is removed in the following bath:

G. Potassium ferricyanide 50 Potassium bromide 3 Water to 1000 ccm.

After this removal of the silver, which also oxidizes the coupler residue, the material is washed again for 10 minutes and next fixed for 20 minutes in a bath composed of 250 g. sodium thiosulphate in 1000 ccm. water and finally washed for 30 minutes. A blue-green devel oped image and an orange-red complementary image were obtained.

Example 5 A multi-layer material is made by employing the usual arrangement of sensitive layers as follows:

(1) Film base or other suitable support,

(2) silver halide emulsion layer sensitized to red by known means, and containing 5 g. per litre emulsion of the cyan color coupler described in Example 9 of Patent No. 2,186,849,

(3) silver halide emulsion layer sensitized to green by known means and to which per litre emulsion are added 5 g. of the magenta color coupler according to Example 1 dissolved in 20 ccm. of an aqueous solution of potassium hydroxide N, 20 ccm. methanol and 100 ccm. water,

(4) yellow filter layer containing yellow colloidal silver as known in the art,

(5) unsensitized silver halide emulsion layer containing 5 g. of the yellow color coupler described in Example 2, 3 or 4 of application Serial No. 62,967,. filed December 1, 1948, applicant Philibert L. .Merckx, now abandoned.

The above material is exposed and developed with a solution obtained by mixing equal parts of the: following solutions G. NzNwliethybp-phenyleue diamine hydrochloride -6 1 The time of development will depend upon the nature of the particular silver halide emulsions employed.

After washing for 30 minutes, the silver is removed in the following bath:

- G. Potassium ferricyanide 50 Potassium bromide 3 Water to 1000 ccm.

After this removal'of the silver, which also oxidizes the residual magenta color coupler, the material is again washed for minutes and next fixed for minutes in a bath composed of 250 g. sodium thiosulphate in 1-000 ccm. water and finally washed for minutes. A

multi-color image and a yellow complementary image in the middle layer were obtained.

Example 6 is obtained. A multilayer material is made by employing the usual arrangement of sensitive layers as follows:

p (1) Film base or other suitable support.

(2) silver halide emulsion layer sensitized to red by known means and containing 5 g. per litre emulsion of the cyan color coupler corresponding to the Formula lX (IX) OH dissolved in ccm. methanol and 20 ccm. triethanol amine,

(3) silver halide emulsion layer sensitized to green by known means and to which per litre of emulsion are added 5 g. of the magenta color coupler according to Example 1 dissolved in 20 ccm. of an aqueous solution of potassium hydroxide N, 20 ccm. methanol and 1000 ccm. water,

(4) yellow filter layer containing yellow colloidal silver as known from the prior art,

(5) unsensitized silver halide emulsion layer containing 5 g. of the yellow color coupler described in Example 2, 3 or 4 of the above referred to application Serial No. 62,967.

The above material is exposed and developed with a solution obtained by mixing equal parts of the following solutions:

Water to 500 ccm.

' The time of development will depend upon the nature of the particular silver halide emulsions employed.

After washing for 30 minutes, the silver is removed in the following bath:

. G. Potassium terricyanide 50 Potassium bromide 3 Water to 1000 ccm.

After this removal of the silver, which also oxidizes the residual magenta and cyan color couplers, the material is again washed for 10 minutes and next fixed for 20 minutes in a bath composed of 250 g. sodium thiosulphate in 1000 ccm. water and finally washed for 30 minutes. A multi-color image, a yellow complementary image in the middle layer (3) and an orange complementary image in the lower layer (2) were obtained.

l claim:

1. Process for the production of a photographic multicolored image, which comprises exposing to light a photo graphic material containing at least two silver halide emulsion layers sensitive to different regions of the visible spectrum, at least one of these layers containing a color coupler which is able to form, by reaction with the oxidation product of a primary aromatic amino developing agent, a dyestuft" image undesirably absorbing in the blue region of the visible spectrum and more strongly absorbing in another part of the visible spectrum, and which color coupler by oxidation is converted into a blue-absorbing colored substance practically not absorbing in said other part of the visible spectrum, which process further comprises developing at least that layer containing said color coupler with a primary aromatic amino developing agent, and treating at least the remaining color coupler of this layer in an oxidizing bath, said color coupler containing a -NH-NH-CA- group within a ring, wherein A is a member selected from the group consisting of O, NH, N linked to a hydrocarbon radical, and N linked to an acyl group.

2. Process for the production of a photographic multicolored image, which comprises exposing to light a photographic material containing three silver halide emulsion layers sensitive to different regions of the visible spectrum, one of these layers being sensitive to blue light only and containing a yellow color coupler, another of the three layers being sensitive to green light only and containing a magenta color coupler which, by oxidation, is converted into a yellow product, the third of said layers being sensitive to red light only and containing a cyan color coupler which, by oxidation, is converted into a substance selected from the group consisting of red, orange and yellow substances, which process further comprises developing that material with a primary aromatic amino developing agent, and treating it in an oxidizing bath, said color coupler containing a NHNHCA-- group within a ring, wherein A is a member selected from the group consisting of O, NH, N linked to a hydrocarbon radical, and N linked to an acyl group.

3. Process for the production of a photographic multicolored image, which comprises exposing to light a photographic material containing three silver halide emulsion layers sensitive to diiierent regions of the visible spectrum, one of these layers being sensitive to blue light only and containing a yellow color coupler, another of the three layers being sensitive to blue and green light and containing a magenta color coupler which, by'oxidation, is converted into a yellow product, the third of the three layers being sensitive to blue and red light and containing a cyan color coupler which, by oxidation, is converted into a substance selected from the group consisting of red, orange and yellow substances, said material further containing a yellow filter layer between the layer sensitive to blue only and the other sensitive layers, which process further comprises developing that material 'with a primary aromatic amino developing agent, and treating it in an oxidizing bath, said color 9 coupler containing a --NH--NHCA- group within a ring, wherein A is a member selected from the group consisting of O, NH, N linked to a hydrocarbon radical, and N linked to an acyl group.

4. Photographic material which comprises at least two silver halide emulsion layers sensitive to different regions of the visible spectrum, at least one of these layers containing a color coupler which is able to form, by reaction with the oxidation product of a primary aromatic amino developing agent, a dyestuff image undesirably absorbing in the blue region of the visible spectrum and more strongly absorbing in another part of the visible spectrum, and which color coupler by oxidation is converted into a blue-absorbing colored substance practically not absorbing in said other part of the visible spectrum, said color coupler, moreover, containing, a -NHNH-CA- group within a ring, wherein A is a member selected from the group consisting of O, NH, N linked to a hydrocarbon radical, and N linked to an acyl group.

5. Photographic material which comprises three silver 20 halide emulsion layers sensitive to different regions of the visible spectrum, one of said layers being sensitive to blue light only and containing a yellow color coupler, another of the three layers being sensitive to green light only and containing a magenta color coupler which, by oxidation, is converted into a yellow product, the third of said layers being sensitive to red light only and containing a cyan color coupler which, by oxidation, is converted into a substance selected from the group consisting of red, orange and yellow substances, said color coupler, moreover, containing a NH-NHCA-- group within a ring, wherein A is a member selected from the group consisting of O, NH, N linked to a hydrocarbon radical, and N linked to an acyl group.

5 another of the three layers being sensitive to blue and green light and containing a magenta color coupler which, by oxidation, is converted into a yellow product, the third of the three layers being sensitive to blue and red light and containing a cyan color coupler which, by

10 oxidation, is converted into a substance selected from the group consisting of red, orange and yellow substances, said material further containing a yellow filter layer between the layer sensitive to blue only and the other sensitive layers, said color coupler, moreover, containing a 5 NHNH-CA- group within a ring, wherein A is a member selected from the group consisting of O, NH, N linked to a hydrocarbon radical, and N linked to an acyl group.

References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Hackhs Chemical Dictionary, Grant, 3rd ed., 1950;

30 publ. by the Blakiston C0., Philadelphia, page 698.

Organic Chemistry, Karrer, 2nd English ed., 1946, publ. by Elsevier Publ. C0., New York, page 773. 

1. PROCESS FOR THE PRODUCTION OF A PHOTOGRAPHIC MULTICOLORED IMAGE, WHICH COMPRISES EXPOSING TO LIGHT A PHOTOGRAPHIC MATERIAL CONTAINING AT LEAST TWO SILVER HALIDE EMULSION LAYERS SENSITIVE TO DIFFERENT REGIONS OF THE VISIBLE SPECTRUM, AT LEAST ONE OF THESE LAYERS CONTAINING A COLOR COUPLER WHICH IS ABLE TO FORM, BY REACTION WITH THE OXIDATION PRODUCT OF A PRIMARY AROMATIC AMINO DEVELOPING AGENT, A DYESTUFF IMAGE UNDESIRABLY ABSORBING IN THE BLUE REGION OF THE VISIBLE SPECTRUM AND MORE STRONGLY ABSORBING IN ANOTHER PART OF THE VISIBLE SPECTRUM, AND WHICH COLOR COUPLER BY OXIDATION IS CONVERTED INTO A BLUE-ABSORBING COLORED SUBSTANCE PRACTICALLY NOT ABSORBING IN SAID OTHER PART OF THE VISIBLE SPECTRUM, WHICH PROCESS FURTHER COMPRISES DEVELOPING AT LEAST THAT LAYER CONTAINING SAID COLOR COUPLER WITH A PRIMARY AROMATIC AMINO DEVELOPING AGENT, AND TREATING AT LEAST THE REMAINING COLOR COUPLER OF THIS LAYER IN AN OXIDIZING BATH, SAID COLOR COUPLER CONTAINING A -NH-NH-CA- GROUP WITHIN A RING, WHEREIN A IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF O, NH, N LINKED TO A HYDROCARBON RADICAL, AND N LINKED TO AN ACYL GROUP. 